Isolation of para-xylene



EN'l cries ISOLATIQN F PARAJIYLENE Richard B. Greenliurg Mclrose Park, Pa, assignor to Allied Chemical & Dye Corporation, New York, N. Y., a corporation of New York No Drawing. Application August 7, 1943,

Serial No. 497,871 a 9 Claims. (CL 260-674) This invention relates to the separation of parphase are advantageously carried out successiveaxylene from mixtures thereof with other xylenes. ly in a plurality of alternate operations.

Xylenes are obtained commercially from var- The combined steps of solidifying or partially ious natural sources such as coke-oven distillate solidifying the xylene mixture in the presence of and drip oil (the oil which accumulates in gas methanol or ethanol and fractional melting of mains). A xylene oil thus obtained ordinarily the solid thus formed in a plurality of stages with contains all three xylenes. A reasonably effective removal of melted material resulting from each separation of ortho-xylene from this mixture may fractional melting operation, I have found, surbe made by fractionation of the xylene mixture. prisingly makes it possible to withdraw as a prod- Metaand paraxylenes, however, are so close in 10 not from the melting of the final portion of solid boiling points that fractionation is inefiective to a material that consists of substantially 100% bring about separation. pure paraxylene. The mechanism of this process It has been proposed to bring about separation is not fully understood, but the use of methanol of metaand paraxylenes by a method involving or ethanol rather than any other diluent durin the selective sulfonation of the metaxylene concooling of the mixture to produce a solid phase tent of the mixture, separation of the sulfonated appears to be an important factor in forming a metaxylene from the unsulfonated oil containing solid of such characteristics that 100% pure parprimarily paraxylene, sulfonation of the paraxyaxylene can be withdrawn as the final fraction lene-containing oil,raddition of hydrochloric acid upon fractional melting of the solid material. to the latter sulfonation product to precipitate The process of my invention may be applied to paraxylene sulfonic acid, washing of the preciplany industrial xylene mixture that contains more tate with hydrochloric acid, and hydrolysis of than 16% paraxylene, prefera ly at least a out the resulting paraxylene sulfonic acid. Methods 2 paraxylene, th r m n er being Pre mof this type described in the published prior art, inantly metaxy n f r, pl the Xylene freohowever, are unsatisfactory because they require tion of coke-oven distillates, drip watera very lengthy sulfonation process, the sulfonatar and oil-gas-tar oils, similar light oils contion is not sufliciently selective, the use of hydrotaining aromatic hydrocarbons, the aromatic oh'loric acid introduces a relatively expensive refraction of petrol hydrocarbons. and other agent and aggravates corrosion conditions, the sources of aromatic hydrocarbons of the benzene yields are low and purity of product is very poor. series c a p ylene source material will It has also been proposed to separate paraxyn a ly c n in ddi i n t the p r xylene. lene, which has the highest melting point of the metaxylene and other close-boiling hydro r xylenes, from a xylene mixture by fractional crysie-, hydrocarbons having bo Points close to tallization thereof. It has been found, however, those of paraand metaxylenes. Examples of that fractional crystallization produces a product such other hydrocarbons in e thoxylene. that contains metaxylene admixed with paraxyethylbenzene, and paraflin hydrocarbons of about lene, and to prepare pure paraxylene'by such a he some il n p n as p xy n A Xy method requires repeated crystallizations. The oil which contains all three xylen s m if eprocess is accordingly unsatisfactory'and expensired, first be fractionated to obtain a fraction slve because of the number of low-temperature to somewhat enriched in paraxylene; the process of crystallization operations involved. I have found my invention. however. is pplicable to any Y- no commercially practicable and economically atlene mixture containing more than 16%, P tractive method suggested in the published prior ably at least about 20%. of paraxylene, the reart for separation of 100% pure paraxylene, mainder being predominantly metaxylene. I

It is an object of this invention to provide a have found it advantageous to employ in the practicable process for separating pure paraxyprocess of my invention the commercially availlene in good yield from a mixture of xylenes. able Xylene that consists chiefly of metaand I have discovered that pure paraxylene may x n e pr p i n o m -Xyl e pr be readily separated in good yield from a mixdominating over p axylene but the latter being ture of xylenes that contains more than 16% present in amount over 16%. For example, ni-

I paraxylene by adding methanol or ethanol to the i -h n X e refined metaand par xy n xylene mixture, cooling the resulting xylene-alcom x re iling from about 138 to 140 0;; low in hol solution sumciently to solidify at least part p n ro n is a commercially availof the xylene mixture, thereafter fractionally able xylene mixture that may be advantageously melting the solid hydrocarbon mixture and, at a r d y t pr f my nv tion.

plurality of temperatures during this fractional Sinc h Process of my n n n produces a melting, removing liquid phase material formed 100% p paraxylene, it y also e vantaby the fractional melting while a part of the hyeously applied o pr p rin p yl n drocarbon mixture remains in the solid state. from the paraxylene generally of to 98% The fractional melting. and removal of liquid to purity, produ d y s o t n th ds of s a-- arating metaand paraxylenes. However, my process is generally applied to a xylene oil containing less than these proportions of paraxylene.

In practicing my invention a mixture of xylenes and other close-boiling hydrocarbons containing more than 16% paraxylene, for example the readily available nitration xylene containing about 20% paraxylene, about 50% metaxylene, about 20% orthoxylene and'a few percent of other hydrocarbons such as paraflins and ethylbenzene, is admixed with ethanol or methanol. The amount of alcohol may range from about 20% to 80% by volume, based on the hydrocarbon, the amount employed being dependent upon the amount of paraxylene present and the amount and purity of the product desired; 1 have found that equal proportions of alcohol and hydrocarbon by volume are generally advantageous.

The alcohol-xylene mixture is then cooled, preferably to a temperature of between -65 and -'70 C., at which temperature substantially all or the greater part of the paraxylene, admixed with other hydrocarbons, has solidified, and the alcohol is largely .in the liquid phase. Alternatively, the mixture may be sufllciently cooled to solidify substantially all components, and may then be warmed slowly so as to bring it to equilibrium at a point where the alcohol is largely in the liquid phase and paraxylene is largely in the solid phase.

The mixture is then subjected to filtration, e. g., by means of an internal filter inserted in the mass or by means of a refrigerated centrifuge, to remove the liquid phase as completely as practicable. This first liquid removed from the mixture, referred to herein, as "mother liquor, generally is made up of alcohol containing dissolved hydrocarbons consisting substantially entirely of metaxylene and other hydrocarbons other than paraxylene.

After removal of the mother liquor, the residual solid is warmed up in a plurality of stages, and melted material resulting from each increase in temperature is removed. Up to about C. the material is advantageously melted in stages representing a rise in temperature of about 20 to 40 C. each; above 0 C. the material may advantageously be melted in stages corresponding to smaller temperature rises, e. g. 5 to each, until all the solid has been melted. As above stated, at the end of each warming stage the mixture is treated to separate as much of the liquid phase as is practicable, for example by use of an inside filter (e. g., in the form of a battery of filter leaves) immersed in the mass or by whirling in a refrigerated centrifuge. Alternatively, the solidified hydrocarbon mixture may be subjected to simultaneous warming and illtration; liquid phase material formed by the fractional melting is thus still removed at a plurality of temperature during the fractional melting.

When the solidified xylene-alcohol mixture is melted and liquid phase material drawn oil as above described, I have found that a 100% pure paraxylene product is recovered from the material melting above about 10 C. The cuts taken just under 10 0., for example material'melting from about 20 to +10 0., I have found, are generally high in paraxylene and may be useful for many purposes where paraxylene of somewhat less than 100% purity can be employed.

"This material may also be reworked with a new charge to obtain an additional yield of 100% paraxylene.

The following examples :reillustrative of the process of the invention:

Examrm 1 50 parts by volume ofa nitration grade xylene containing about 20% paraxylene, about 50% metaxylene, about 25% orthoxylene, and about 5% of other hydrocarbons, chiefly paraflins, were mixed with 50 parts by volume of methanol and the mixture was placed in a refrigerated vessel. An internal filtering unit was immersed in the mixture. This unit was designed so that upon application of vacuum liquid would be drawn from the material in which the unit was immersed through a filter medium into an internal chamber of the filter unit from whence liquid could be withdrawn through a conduit. After immersing a filter unit in the xylene-alcohol mixture the internal chamber of the filter unit was placed under a slight air pressure so as to prevent liquid from seeping into the passages of the filter medium and freezing there when the xylene-alcohol mixture was later cooled. The mixture was cooled to about -'l1 C. and was held at this temperature until equilibrium had been attained. At this point, three-quarters to fourfifths of the xylene-alcohol mixture still remained liquid. Vacuum was then applied to the filter unit and '77 volume parts of liquid, largely the methanol diluent, were drawn oil. The temperature of the residual mixture was permitted to rise and the liquid phase which formed by melting of the solid was drawn off from time to time as completely as possible. In this way, four additional fractions of material were taken off as liquid through the filter by the time the temperature had risen to 17 C. and all solid material had melted.

The data on these cuts are as follows:

50 parts by volume oi the same xylene mixture as in Example 1 were mixed with 50 parts by volume of ethanol. This mixture was treated as described in Example 1 except that it was initially cooled to 68 rather than -'71 C. and the temperature of the mixture was permitted to rise to -64.5 C. while the mother liquor was being taken off.

The data on this run are as follows:

Table 2 Temperature at which removed Volume per cent of charge taken as cut Volume per cent paraxylene in cut Cut No.

C'. -68 to 64. 5 64. 5 to -20 -20 to 0 The expression "alkanol of not more than 2 carbon atoms" is used in the claims to denote either methanol or ethanol.

not more than 2 carbon atoms to solidify at least a part of the hydrocarbon mixture, thereafter fractionally melting the solid hydrocarbon mixture' and, at a plurality of temperatures during said fractional melting, removing liquid phase material formed by the fractional melting.

2. In a process for separating pure paraxylene from a mixed xylene oil containing more than 16% paraxylene, the remainder consisting predominantly of metaxylene, the steps that comprise cooling a mixture of said oil and an alkanol of not more than 2 carbon atoms to solidify at least a part 01' the hydrocarbon mixture, thereafter fractionally melting the solid hydrocarbon mixture and, at a plurality of temperatures during said fractional melting, removing liquid phase material formed by the fractional melting while a part of the hydrocarbon mixture remains in the solid state.

3. In a process for separating pure paraxylene from amixed iwlene oil containing more than 16% paraxylene, the remainder consisting predominantly of metaxylene, the steps that comprise cooling a mixture oi said oil and an alkanol or not more than 2 carbon atoms to solidify at least a part of the hydrocarbon mixture, and thereafter, in a plurality of stages of alternate operations, successively removing liquid phase and melting a part of the solid to form additional liquid phase until the mixture reaches a temperature of about C., removing melted material resulting from each increase in temperature up to a temperature of about +10 C., and withdrawing as substantially pure paraxylene product the material melting above +10 C.

4. In a process for separating pure paraxylene from a mixed xylene oil containing more than 16% paraxylene, the remainder consisting predominantly Oi metaxylene, the steps that comprise cooling a mixture of said oil and ethyl alcohol to solidify at least a part of the hydrocarbon mixture, and thereafter, in a plurality of stages of alternate operations, successively removing liquid phase and melting a part or the I solid to term additional liquid phase, whereby substantially pure paraxylene is withdrawn as the final melting fraction.

5. In a process for separating pure paraxylene from a mixed xylene oil containing more than 16% paraxylene, the remainder consisting predominantly oi metaxylene, the steps that comprise cooling a mixture oi said oil and methyl alcohol to solidify at least .a part of the hydrocarbon mixture, and thereafter, in a plurality of stages of alternate operations, successively removing liquid phase and melting a part oi the solid to form additional liquid phase, whereby substantially pure paraxylene is withdrawn as the final melting fraction,

6. In a process 501' separating pure paraxylene about 20% paraxylene, the remainder consisting predominantly oi metaxylene, the steps that comprise cooling a mixture or said oil and from about 20% to about by volume, based on the oil, oi an alkanol 01 not more than 2 carbon atoms, to solidify at least a part or the hydrocarbon mixture, thereaiter allowing the temperature of the mixture to rise in a series of steps, removing melted material resulting from each increase in temperature up to a temperature of about +10 C., and withdrawing as substantially pure paraxylene product the material melting above +10 C.

7. In a' process for separating substantially pure paraxylene'irom a mixture of xylenes containing more than 16% paraxylene, the remainder consisting predominantly of metaxylene, the steps that comprise diluting the xylene mixture with an alkanol 01' not more than 2 carbon atoms, bringing the resulting xylene-alcohol solution to a temperature at which a solid phase comprising at least a part of the xylene mixture is in substantial equilibrium with a liquid phase, removing at least a part of said liquid phase, thereafter raising the temperature of the residual mixture in a plurality oi! steps to melt solid and form additional liquid phase, removing melted material resulting from each increase in temperature, and continuing these alternate operations until the residual material consists of substantiaiiy pure paraxylene.

8. In a process for separating substantially pure paraxylene irom a mixture of xylenes containing more than 16% paraxylene, the remainder consisting predominantl of metaxylene, the steps that comprise diluting the iwlene mixture with an alkanol or not more than 2 carbon atoms employed in amount ranging from about 20% to 80% by volume based on the xylene "mixture, bringing the resulting xylene-alcohol solution to a temperature at which a solid phase comprising at least a part of the xylene mixture is in substantial equilibrium with a liquid phase, removing at least a part of said liquid phase, thereafter raising the temperature of the residual mixture Y in a series of steps to melt solid and form additional liquid phase, removing melted material resulting irom each increase in temperature, and continuing these alternate operations until the residual material consists of substantially pure paraxylene.

9. In a process for separating substantially pure paraxylene from a mixture of xylenes containing at least about 20% paraxylene, the remainder consisting predominantly of metaxylene, the stepscomprising diluting the xylene mixture with an alkanol of not more than 2 carbon atoms employed in an amount about equal in volume to the hydrocarbon oil, i in the resulting xylene-alcohol solution to a temperature below about -65 C. at which a solid hydrocarbon phase is in substantial equilibrium with a liquid phase, removing the greater part of said liquid phase, thereafter raising the temperature of the residual mixture in a series 0! stages, each stage involving a temperature increase oi not more than 40 C., to melt solid and form additional liquid phase, removing melted material resulting from each increase in temperature up to a temperature of about +10 C., and withdrawing as substantially pure paraxylene product the material melting above +10 C.

RICHARD B. GREEN'BURG. 

